Planarity of heteroaryldithiocarbazic acid derivatives showing tuberculostatic activity. IV. Diesters of benzoylcarbonohydrazonodithioic acid

Article abstract of DOI:10.1107/S0108270112001734

Dimethyl (3,4-dichloro-benzo-yl)carbonohydrazonodithio-ate, C ₁₀H₁₀Cl₂N₂OS₂, (D1), dibenzyl (3,4-dichloro-benzo-yl)car-bono-hydrazonodithio-ate, C ₂₂H₁₈Cl₂N₂OS₂, (D2), dimethyl (3,4-dichloro-benzo-yl)-1-methyl-carbonohydrazonodithio-ate, C ₁₁H₁₂Cl₂N₂OS₂, (D3), 3,4-dichloro-N′-(1,3-dithio-lan-2-yl-idene)-N-methyl-benzohydrazide, C₁₁H₁₀Cl₂N₂OS₂, (D4), were synthesized as potential tuberculostatics. Compound (D1) (with two molecules in the asymmetric unit) was the only one showing tuberculostatic activity of the same range as the common drugs isoniazid and pyrazinamide. The mol-ecular structures of the studied compounds depend on the substitution at the N atom adjacent to the carbonyl group. In the case of the unsubstituted derivatives (D1) and (D2), their central frames are generally planar with a twist of the 3,4-dichloro-phenyl ring by 30-40°. Until now, coplanarity of the aromatic ring with the (methyl-ene)carbonohydrazone fragment has been considered a prerequisite for tuberculostatic activity. The N-methyl-ated derivatives (D3) and (D4) show an additional twist along the N - C(=O) bond by 20-30° due to the spatial repulsion introduced by the methyl substituent.

Full text of DOI:10.1107/S0108270112001734

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
Several crystal structures of selected representatives of
these compounds were determined by our group in a search
for relationships between activity and molecular structure
´
ISSN 0108-2701
(Głowka et al., 2005; Olczak et al., 2007, 2011; Szczesio et al.,
2011). The main working hypothesis tested in these studies
was that planarity of a molecule is a prerequisite for tuber-
culostatic activity (Olczak et al., 2007). The hypothesis was
based on an observation from our very first study on the
molecular structure of 2-[amino(pyridine-2-yl)methylene]-
hydrazinecarbodithioic acid methyl ester in the crystalline
Planarity of heteroaryldithiocarbazic
acid derivatives showing tuberculo-
static activity. IV. Diesters of
benzoylcarbonohydrazonodithioic
acid1
´
state (Głowka et al., 2005). This active compound in the crystal
state exists in the zwitterionic form (formula A in Scheme 1)
and it is planar (except for the terminal ester group) due to
´
conjugations and intramolecular hydrogen bonds (Głowka et
Małgorzata Szczesio,a Andrzej Olczak,a Katarzyna
al., 2005; Olczak et al., 2007; Orlewska et al., 2001). Surpris-
ingly, overall planarity was also observed in the crystals
of [amino(pyrazin-2-yl)methylene]carbonohydrazonodithioic
acid diesters showing tuberculostatic activity (formula B in
Scheme 1) (Olczak et al., 2011). Owing to the lack of an H
atom at N3, the same intramolecular hydrogen-bond contacts
as those observed in all type A (Scheme 1) structures could
not be formed. Instead, another intramolecular hydrogen
contact was observed, i.e. that between the amine group as a
donor and the N atom at the ortho position of the pyrazine
ring as an acceptor, similar to that observed in all pyrazin-
amide structures [Cambridge Structural Database (CSD),
Version 5.32; Allen, 2002]. In the case of type B compounds
(Scheme 1), planarity of the central structure frame (as
evidenced by the torsion angle at the N—N bond) was secured
by the conjugation alone (Olczak et al., 2011).
b
b
a
´
Gobis, Henryk Foks and Marek L. Głowka *
a
´
´
Institute of General and Ecological Chemistry, Technical University of Łodz, Poland,
b
´
and Department of Organic Chemistry, Medical University of Gdansk, Poland
Correspondence e-mail: marek.glowka@p.lodz.pl
Received 25 November 2011
Accepted 14 January 2012
Online 4 February 2012
Dimethyl (3,4-dichlorobenzoyl)carbonohydrazonodithioate,
C10H10Cl2N2OS2, (D1), dibenzyl (3,4-dichlorobenzoyl)car-
bonohydrazonodithioate, C22H18Cl2N2OS2, (D2), dimethyl
(3,4-dichlorobenzoyl)-1-methylcarbonohydrazonodithioate,
C11H12Cl2N2OS2, (D3), 3,4-dichloro-N0-(1,3-dithiolan-2-yl-
idene)-N-methylbenzohydrazide, C11H10Cl2N2OS2, (D4),
were synthesized as potential tuberculostatics. Compound
(D1) (with two molecules in the asymmetric unit) was the only
one showing tuberculostatic activity of the same range as the
common drugs isoniazid and pyrazinamide. The molecular
structures of the studied compounds depend on the substitu-
tion at the N atom adjacent to the carbonyl group. In the case
of the unsubstituted derivatives (D1) and (D2), their central
frames are generally planar with a twist of the 3,4-dichloro-
phenyl ring by 30–40ꢀ. Until now, coplanarity of the aromatic
ring with the (methylene)carbonohydrazone fragment has
been considered a prerequisite for tuberculostatic activity. The
N-methylated derivatives (D3) and (D4) show an additional
twist along the N—C( O) bond by 20–30ꢀ due to the spatial
repulsion introduced by the methyl substituent.
Comment
Because of the emergence of multi-drug-resistant strains of
Mycobacterium tuberculosis in developed countries, significant
efforts have been put into a search for new lead tuberculo-
statics. Among others, Foks and coworkers have synthesized
hundreds of compounds, many of which showed reasonable
activity against tuberculosis (Pancechowska-Ksepko et al.,
1993; Milczarska et al., 1998, 1999; Foks et al., 2002; Gobis et al.,
2011).
Next, the amine function in compounds of the types A and
B has been replaced by a carbonyl group (compounds type C
in Scheme 1), with some of the resulting structures also
showing promising activity (Foks et al., 2004; Sitarz et al.,
1 For Part III, see Szczesio et al. (2011).
Acta Cryst. (2012). C68, o99–o103
doi:10.1107/S0108270112001734
# 2012 International Union of Crystallography o99

organic compounds
Figure 3
The molecular structure of (D3), showing the atom-labelling scheme.
Displacement ellipsoids are drawn at the 50% probability level and H
atoms are shown as small spheres of arbitrary radii.
Figure 1
The molecular structure of the two independent molecules of (D1),
showing the atom-labelling scheme. Displacement ellipsoids are drawn at
the 50% probability level and H atoms are shown as small spheres of
arbitrary radii.
We report here a study on the crystal structures of four type
D compounds, (D1)–(D4) (Figs. 1–4), which differ in the ester
groups (methyl, benzyl or cyclic) or in the substitution by the
methyl group at the N3 atom (see Scheme 2). There are seven
diesters of benzoylcarbonohydrazonodithioic acid (CSD,
Version 5.32; Allen, 2002). All are unsubstituted at the N3
atom. However, no mention has been made of their tubercu-
lostatic activity in the literature.
Figure 2
The molecular structure of (D2), showing the atom-labelling scheme.
Displacement ellipsoids are drawn at the 50% probability level and H
atoms are shown as small spheres of arbitrary radii.
2005). This was in accord with our hypothesis as the
compounds could form similar intramolecular hydrogen bonds
as in compounds of type A. The overall planarity of the
molecules was confirmed in our studies on their crystal
structures (Szczesio et al., 2011).
In accord with our expectation, replacement of the aromatic
ring containing an N atom in the ortho position by a phenyl
ring resulted in its significant twist of 30–40ꢀ in comparison
with planar 2-pyrazine or 2-pyrazine derivatives studied
earlier. Similar values are observed in 19 benzamide structures
found in the CSD, with an average of 22ꢀ (CSD, Version 5.32;
Allen, 2002).
The other significant difference in the molecular structures
of the D type and the formerly studied C type (Szczesio et al.,
2011) compounds is the conformation around the N2—N3
bond. The absolute values of the respective C1 N2—N3—C4
torsion angles are close to 177ꢀ in two planar diesters of
(pyrazine-2-carbonyl)carbonohydrazonodithioic acid (type C)
(Szczesio et al., 2011) as compared with values of 166.39 (15)ꢀ
in (D2), ꢂ139.31 (18) and ꢂ150.87 (17)ꢀ in (D1), 131.65 (16)ꢀ
in (D3) and 126.49 (17)ꢀ in (D4) (Table 1). The lack of an H
atom at the N3 atom in (D3) and (D4) also results in their very
Our earlier observation that the conjugation in type B
compounds was sufficient to secure planarity of the central
molecular chain prompted us to synthesize the respective
analogues D (Scheme 1), in which we have removed the final
possibility of keeping the aromatic ring coplanar with the
hydrazide fragment due to the intramolecular N5—Hꢁ ꢁ ꢁ
N(ring) hydrogen bond (formula D in Scheme 1). We were
encouraged by the structural characteristics of the well known
agent isoniazid, in which this intramolecular hydrogen bond
could also not be formed (Scheme 1). Most of the type B
compounds show weak tuberculostatic activity [minimum
inhibitory concentration (MIC) about 50 mg mlꢂ1] but for
some the values are 20 times lower (Foks et al., 1992; Orlewska
et al., 1995).
ꢃ
o100 Szczesio et al. C10H10Cl2N2OS2, C22H18Cl2N2OS2, C11H12Cl2N2OS2 and C11H10Cl2N2OS2
Acta Cryst. (2012). C68, o99–o103

organic compounds
Figure 4
The molecular structure of (D4), showing the atom-labelling scheme.
Displacement ellipsoids are drawn at the 50% probability level and H
atoms are shown as small spheres of arbitrary radii.
Figure 6
The intermolecular hydrogen bonds of (D2) determining the packing of
1
molecules in the crystal. [Symmetry code: (i) x, ꢂy, z ꢂ .]
2
ꢀ
˚
ꢂ140 and ꢂ150 ) in (D1) and 1.3703 (18) A (torsion about
166ꢀ) in (D2) due to increasing (in the listed order) p(N3)–
p(N2 C1) conjugation for the antiperiplanar (torsion about
180ꢀ) conformation.
Another interesting issue concerns the intramolecular N3—
Hꢁ ꢁ ꢁS hydrogen-bond contact possible in (D1) and (D2).
˚
Although the Hꢁ ꢁ ꢁS distances of 2.49 and 2.52 A in (D1) and
˚
2.59 A in (D2) are significantly shorter than the sum of their
˚
van der Waals radii (2.89 A), the angles at the H atom are only
104, 99 and 108ꢀ, respectively. So, despite the Hꢁ ꢁ ꢁS distances
indicating hydrogen bonds, there is some doubt in the litera-
ture concerning contribution of the contacts to the stabiliza-
tion energy of the crystals, especially because of the low values
of the N3—Hꢁ ꢁ ꢁS angles (Wood et al., 2009; Galek et al., 2010;
Bilton et al., 2000). Our view on the subject has been presented
in Szczesio et al. (2011).
Figure 5
The intermolecular hydrogen bonds of (D1) determining the packing of
molecules in the crystal. [Symmetry codes: (i) x + 1, y, z + 1; (ii) x ꢂ 1, y,
z.]
In the studied crystals there are several intermolecular
hydrogen bonds, some of which are quite strong and important
for crystal packing (Figs. 5–7). In (D1), the two independent
molecules form an infinite C22(8) chain [according to the
graph-set definition of Bernstein et al. (1995)] parallel to the
[100] direction through two intermolecular hydrogen bonds,
viz. N3—Hꢁ ꢁ ꢁO5A and N3A—Hꢁ ꢁ ꢁO5(x ꢂ 1, y, z). In addi-
tion, in (D1), there exists a C21—Hꢁ ꢁ ꢁCl4A(x + 1, y, z + 1)
different conformation around their N3—C4 bonds in com-
parison with N3-unsubstituted aroylcarbonohydrazonodi-
thioic acid esters (Table 1). The crucial N2—N3—C4—C41
torsion angle is about 180ꢀ in (D1) and (D2) and only 21–31ꢀ
in (D3) and (D4), due to spatial repulsion introduced by the
methyl group in the latter structures. A similar difference is
seen in the related N2—N3—C4 O5 torsion angle, being
about 4ꢀ in (D1) and (D2), and about 155ꢀ in (D3) and (D4)
(Table 1).
The question arises whether the observed differences in the
molecular structures may be related to low tuberculostatic
activity of the N3-substituted compounds. The fact is that only
N3-unsubstituted derivatives show higher activity, especially
(D1) (Gobis et al., 2011).
The differences in conformations along the main chain
correlate with differences in the respective bond lengths
(Table 1) indicating the change in conjugations. The largest
difference is found for the N2—N3 bond length, which is
Figure 7
The intermolecular hydrogen bonds of (D3) determining the packing of
molecules in the crystal. [Symmetry code: (i) x, y + 1, z.]
ꢀ
˚
ꢀ
˚
1.435 (2) A (torsion about 130 ) in (D3), 1.433 (2) A (torsion
˚
about 125 ) in (D4), 1.416 (2) and 1.402 (2) A (torsion about
ꢃ
Acta Cryst. (2012). C68, o99–o103
Szczesio et al.
C10H10Cl2N2OS2, C22H18Cl2N2OS2, C11H12Cl2N2OS2 and C11H10Cl2N2OS2 o101

organic compounds
Table 1
Selected bond lengths (A) and torsion angles ( ) for the title compounds.
contact taking part in the formation of two additional chains,
viz. C22(14) parallel to the [101] direction with an N3—
Hꢁ ꢁ ꢁO5A hydrogen bond and C22(16) parallel to the [001]
direction with an N3A—Hꢁ ꢁ ꢁO5(x ꢂ 1, y, z) hydrogen bond.
At the third level of the graph-set theory, the R66(38) ring
formed by N3—Hꢁ ꢁ ꢁO5A, N3A—Hꢁ ꢁ ꢁO5(x ꢂ 1, y, z) and
C21—Hꢁ ꢁ ꢁCl4A(x + 1, y, z + 1) can be identified (Fig. 5). In
(D2), there is only one weak hydrogen bond, C16—Hꢁ ꢁ ꢁO5(x,
ꢀ
˚
C1—N2—N3—C4 N2—N3—C4—C41 N2—N3—C4—O5 N2—N3
(D1) ꢂ139.31 (18)
ꢂ150.87 (17)
ꢂ177.95 (16)
ꢂ178.19 (15)
177.63 (13)
ꢂ31.2 (2)
4.0 (3)
3.1 (3)
ꢂ4.1 (2)
152.86 (16)
159.99 (18)
1.416 (2)
1.402 (2)
1.3703 (18)
1.435 (2)
1.433 (2)
(D2)
(D3)
(D4)
166.39 (15)
131.65 (16)
126.49 (17)
ꢂ21.1 (2)
1
2
ꢂy, z ꢂ ), forming a C(11) chain parallel to the [001] direction
(Fig. 6). In (D3), there is also one weak hydrogen bond, C11—
Hꢁ ꢁ ꢁO5(x, y + 1, z), forming a C(8) chain parallel to the [010]
direction (Fig. 7). No significant intermolecular contacts were
observed in (D4).
Table 2
Hydrogen-bond geometry (A, ) for (D1).
ꢀ
˚
D—Hꢁ ꢁ ꢁA
D—H
Hꢁ ꢁ ꢁA
Dꢁ ꢁ ꢁA
D—Hꢁ ꢁ ꢁA
C21—H21Eꢁ ꢁ ꢁCl4Ai
N3A—H3Aꢁ ꢁ ꢁO5ii
N3—H3ꢁ ꢁ ꢁO5A
N3—H3ꢁ ꢁ ꢁS1
0.96
0.86
0.86
0.86
0.86
2.75
2.10
2.06
2.52
2.49
3.565 (3)
2.8434 (18)
2.834 (2)
2.7810 (17)
2.8216 (16)
144
144
149
99
Experimental
The synthesis of (D1) was described previously by Gobis et al. (2011).
The other compounds were obtained from 3,4-dichlorobenzohydra-
zide [for (D2)] or 3,4-dichloro-N-methylhydrazide [for (D3) and
(D4)] according to the same method. Benzohydrazides were dissolved
in a methanol solution of triethylamine and treated with carbon
disulfide and the respective halide, viz. methyl iodide for (D3), benzyl
chloride for (D2) or ethylene bromide for (D4). Single crystals of
(D1), (D2), (D3) and (D4) suitable for X-ray diffraction were
obtained from ethanol solutions by slow evaporation of the solvents
at room temperature.
N3A—H3Aꢁ ꢁ ꢁS1A
104
Symmetry codes: (i) x þ 1; y; z þ 1; (ii) x ꢂ 1; y; z.
Table 3
Hydrogen-bond geometry (A, ) for (D2).
ꢀ
˚
D—Hꢁ ꢁ ꢁA
D—H
Hꢁ ꢁ ꢁA
Dꢁ ꢁ ꢁA
D—Hꢁ ꢁ ꢁA
N3—H3ꢁ ꢁ ꢁS1
0.86
0.93
2.59
2.44
2.9751 (14)
3.294 (3)
108
153
C16—H16ꢁ ꢁ ꢁO5i
1
2
Symmetry code: (i) x; ꢂy; z ꢂ .
Compound (D1)
Crystal data
Table 4
Hydrogen-bond geometry (A, ) for (D3).
ꢀ
˚
3
˚
C10H10Cl2N2OS2
Mr = 309.22
Monoclinic, P21
V = 1354.99 (10) A
Z = 4
Mo Kꢁ radiation
ꢂ = 0.77 mmꢂ1
T = 296 K
D—Hꢁ ꢁ ꢁA
D—H
Hꢁ ꢁ ꢁA
Dꢁ ꢁ ꢁA
D—Hꢁ ꢁ ꢁA
˚
a = 9.2225 (4) A
C11—H11Bꢁ ꢁ ꢁO5i
0.96
2.49
3.200 (2)
131
˚
b = 11.2741 (5) A
˚
c = 13.0892 (5) A
0.3 ꢄ 0.3 ꢄ 0.1 mm
Symmetry code: (i) x; y þ 1; z.
ꢀ = 95.367 (1)ꢀ
Data collection
Bruker SMART APEXII CCD
diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
Tmin = 0.914, Tmax = 1.000
33334 measured reflections
7766 independent reflections
7138 reflections with I > 2ꢃ(I)
Rint = 0.021
Data collection
Kuma KM-4 CCD diffractometer
Absorption correction: multi-scan
(CrysAlis RED; Oxford
Diffraction, 2008)
Tmin = 0.942, Tmax = 1.000
17461 measured reflections
3868 independent reflections
3021 reflections with I > 2ꢃ(I)
Rint = 0.022
Refinement
R[F2 > 2ꢃ(F2)] = 0.033
wR(F2) = 0.092
S = 1.08
7766 reflections
312 parameters
1 restraint
H-atom parameteꢂrs3 constrained
Refinement
˚
Áꢄmax = 0.79 e A
R[F2 > 2ꢃ(F2)] = 0.030
wR(F2) = 0.084
S = 0.94
262 parameters
H-atom parameteꢂrs3 constrained
ꢂ3
˚
Áꢄmin = ꢂ0.31 e A
Absolute structure: Flack (1983),
3697 Friedel pairs
˚
Áꢄmax = 0.22 e A
ꢂ3
˚
3868 reflections
Áꢄmin = ꢂ0.29 e A
Flack parameter: ꢂ0.02 (4)
Compound (D3)
Compound (D2)
Crystal data
Crystal data
C11H12Cl2N2OS2
Mr = 323.25
Triclinic, P1
ꢅ = 74.892 (5)ꢀ
V = 708.08 (7) A
Z = 2
Mo Kꢁ radiation
ꢂ = 0.74 mmꢂ1
T = 291 K
3
3
˚
˚
V = 4376.2 (3) A
Z = 8
C22H18Cl2N2OS2
Mr = 461.40
Monoclinic, C2=c
a = 28.6760 (11) A
˚
a = 8.9307 (4) A
Mo Kꢁ radiation
ꢂ = 0.50 mmꢂ1
T = 292 K
0.55 ꢄ 0.4 ꢄ 0.3 mm
˚
b = 9.0858 (7) A
˚
˚
c = 10.3873 (5) A
˚
b = 10.3705 (3) A
ꢁ = 65.039 (6)ꢀ
ꢀ = 69.172 (4)ꢀ
0.5 ꢄ 0.35 ꢄ 0.2 mm
˚
c = 14.7176 (6) A
ꢀ = 90.900 (4)ꢀ
ꢃ
o102 Szczesio et al. C10H10Cl2N2OS2, C22H18Cl2N2OS2, C11H12Cl2N2OS2 and C11H10Cl2N2OS2
Acta Cryst. (2012). C68, o99–o103

organic compounds
Mercury (Macrae et al., 2006); software used to prepare material for
publication: PLATON.
Data collection
Kuma KM-4 CCD diffractometer
Absorption correction: multi-scan
(CrysAlis RED; Oxford
Diffraction, 2008)
Tmin = 0.447, Tmax = 1.000
10270 measured reflections
2494 independent reflections
2181 reflections with I > 2ꢃ(I)
Rint = 0.034
The present study was supported by the Ministry of Science
and Higher Education under project No. N204 111735.
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: WQ3009). Services for accessing these data are
described at the back of the journal.
Refinement
R[F2 > 2ꢃ(F2)] = 0.033
wR(F2) = 0.097
S = 1.15
166 parameters
H-atom parameteꢂrs3 constrained
˚
Áꢄmax = 0.24 e A
ꢂ3
˚
2494 reflections
Áꢄmin = ꢂ0.42 e A
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Crystal data
3
˚
V = 1425.08 (3) A
Z = 4
Cu Kꢁ radiation
ꢂ = 6.76 mmꢂ1
T = 296 K
C11H10Cl2N2OS2
Mr = 321.23
Monoclinic, P21=c
˚
a = 13.3680 (2) A
˚
b = 8.1817 (1) A
˚
c = 13.5158 (2) A
0.3 ꢄ 0.2 ꢄ 0.05 mm
ꢀ = 105.415 (1)ꢀ
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´
Data collection
´
Bruker SMART APEXII CCD
diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
Tmin = 0.423, Tmax = 0.753
15835 measured reflections
2643 independent reflections
2589 reflections with I > 2ꢃ(I)
Rint = 0.034
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´
´
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˙ ´
Milczarska, B., Foks, H., Trapkowski, Z., Milzynska-Kołaczek, A., Janowiec,
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Refinement
R[F2 > 2ꢃ(F2)] = 0.034
wR(F2) = 0.100
S = 1.06
165 parameters
H-atom parameteꢂrs3 constrained
289–295.
Olczak, A., Głowka, M. L., Gołka, J., Szczesio, M., Bojarska, J., Kozłowska, K.,
˚
Áꢄmax = 0.48 e A
Áꢄmin = ꢂ0.36 e A
´
Foks, H. & Orlewska, C. (2007). J. Mol. Struct. 830, 171–175.
ꢂ3
˚
2643 reflections
Olczak, A., Szczesio, M., Gołka, J., Orlewska, C., Gobis, K., Foks, H. &
´
Głowka, M. L. (2011). Acta Cryst. C67, o37–o42.
Orlewska, C., Foks, H., Janowiec, M. & Zwolska-Kwiek, Z. (1995). Pharmazie,
50, 265–266.
H atoms were located in difference Fourier maps and subsequently
geometrically optimized and allowed for as riding atoms, with C—H =
´
´
Orlewska, C., Foks, H., Sowinski, P., Martynowski, D., Olczak, A. & Głowka,
˚
˚
0.93 A for aromatic CH groups, 0.97 A for secondary CH2 groups and
M. L. (2001). Pol. J. Chem. 75, 1237–1245.
Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford
Diffraction Ltd, Abingdon, Oxfordshire, England.
˚
˚
0.96 A for methyl groups, N—H = 0.86 A and Uiso(H) = 1.5Ueq(C) for
methyl groups or 1.2Ueq(C,N) otherwise.
Pancechowska-Ksepko, D., Foks, H., Janowiec, M. & Zwolska-Kwiek, Z.
(1993). Acta Pol. Pharm. Drug Res. 50, 259–267.
¨
Sheldrick, G. M. (2003). SADABS. University of Gottingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Data collection: APEX2 (Bruker, 2005) for (D1) and (D4);
CrysAlis CCD (Oxford Diffraction, 2008) for (D2) and (D3). Cell
refinement: SAINT-Plus (Bruker, 2008) for (D1) and (D4); CrysAlis
RED (Oxford Diffraction, 2008) for (D2) and (D3). Data reduction:
SAINT-Plus for (D1) and (D4); CrysAlis RED for (D2) and (D3). For
all compounds, program(s) used to solve structure: SHELXS97
(Sheldrick, 2008); program(s) used to refine structure: SHELXL97
(Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and
´
Sitarz, M., Foks, H., Janowiec, M., Zwolska, Z. & Augustynowicz-Kopec, E.
(2005). Chem. Heterocycl. Compd, 41, 200–207.
Spek, A. L. (2009). Acta Cryst. D65, 148–155.
´
Szczesio, M., Olczak, A., Gołka, J., Gobis, K., Foks, H. & Głowka, M. L. (2011).
Acta Cryst. C67, o235–o240.
Wood, P. A., Allen, F. H. & Pidcock, E. (2009). CrystEngComm, 11, 1563–1571.
ꢃ
Acta Cryst. (2012). C68, o99–o103
Szczesio et al.
C10H10Cl2N2OS2, C22H18Cl2N2OS2, C11H12Cl2N2OS2 and C11H10Cl2N2OS2 o103